Drilling composition, process for its preparation, and applications thereof

ABSTRACT

The present invention relates to a drilling composition comprising an organic phase having at least one linear or branched, cyclic or non-cyclic, saturated hydrocarbon, at least one ester, water or aqueous phase, and at least one additive. 
     The present invention additionally relates to the use and preparation of the drilling composition, to a drilling system, to a process for making a borehole, to a process for conveying cuttings, to a process for treating a drill head, and to a process for production of oil and/or gas.

The present invention relates to a drilling composition, to a processfor preparation of a drilling composition, to uses of a drillingcomposition, to a drilling system, to a process for making a borehole,to a process for conveying cuttings, to a process for treating a drillhead, to a process for production of at least one of oil and gas.

In rotary drilling of subterranean wells a drilling fluid, also referredto as drilling mud, is used for various functions, such as suspendingand removing cuttings from the well, controlling formation pressures,sealing permeable formations, maintaining wellbore stability, minimizingformation damage, cooling, lubricating and supporting the bit anddrilling assembly, transmitting hydraulic energy to tools and bit,ensuring adequate formation evaluation, controlling corrosion of thedrilling assembly as far as possible, and facilitating cementing andcompletion of the well. A further, more recent, aspect is minimizing theeffect on the environment.

Drilling fluids are well known from the prior art. They are typicallyclassified according to their base material. In oil base fluids, solidparticles are suspended in oil, and water or brine may be emulsifiedwith the oil, usually assisted by a surfactant, whereby the oil istypically the continuous phase. In water base fluids, solid particlesare suspended in water and oil may be emulsified therewith, usually inthe presence of a surfactant. Oil based drilling fluids are generallyused in the form of invert emulsion muds, where the oil phase typicallyforms the continuous phase. Earlier drilling fluids relied on heavieroils derived from petrochemicals, such as diesel oil. Such oils are nowless favored because of their negative environmental impact and therehave been a number of publications in the last few years proposingbiodegradable drilling fluids or drilling fluid components.

Drilling fluids comprising reduced toxicity hydrocarbon as maincomponent of the oil phase are known, for example from EP 449 257 A2,U.S. Pat. No. 5,569,642 and U.S. Pat. No. 4,787,990. One disadvantage ofsuch systems is, however, that increased amounts of structure buildingagents such as viscosifiers are often required in order to obtainsuitable rheological properties for a drilling fluid.

DE 39 07 391 A1, DE 39 07 392 A1, DE 38 42 703 A1 and DE 38 42 659 A1describe inverse drilling fluids comprising ester as main component ofthe oil phase. These drilling fluids are distinguished by improvedlubricity and biodegradability compared to mineral oil-based drillingfluids.

An object of the present invention was to reduce or even overcome theproblems associated with the prior art.

A further object of the present invention was to provide a compositionsuitable for use as a drilling fluid, preferably for a wide range ofonshore and offshore oilfield applications. The composition shouldpreferably allow faster, more efficient and/or more effective drillingoperations, under a range of operating conditions, as well as helping tocontribute to reduced wear on drilling equipment.

Another object of the present invention was to provide a moreecologically friendly composition suitable for use as an improveddrilling fluid.

Another object of the present invention was to provide a process forpreparation of such a composition.

A contribution to solving at least one the above objects or furtherobjects arising from the state of the art is made by the subject matterof the category-forming claims. Further developments and preferredembodiments are described in the dependent claims.

In particular, a contribution to solving at least one of the aboveobjects is made by a drilling composition comprising

-   I) an organic phase comprising components    -   i. from about 20 wt. % to about 99.999 wt. %, preferably from        about 40 wt. % to about 99.990 wt. %, preferably from about 60        wt. % to about 99.900 wt. %, preferably from about 70 wt. % to        about 99 wt. %, more preferably from about 80 wt. % to about        98.5 wt. %, yet more preferably from about 85 wt. % to about 98        wt. %, even more preferably from about 90 wt. % to about 98 wt.        %, more preferably from about 92 wt. % to about 97 wt. %, most        preferably from about 93 wt. % to about 96 wt. %, based on the        total weight of components i. and ii., of at least one linear or        branched, cyclic or non-cyclic, saturated hydrocarbon,    -   ii. from about 0.001 wt. % to about 25 wt. %, preferably from        about 0.5 wt. % to about 20 wt. %, more preferably from about 1        wt. % to about 15 wt. %, yet more preferably from about 2 wt. %        to about 10 wt. %, even more preferably from about 2 wt. % to        about 8 wt. %, more preferably more preferably from about 3 wt.        % to about 7 wt. %, most preferably from about 4 wt. % to about        7 wt. %, based on the total weight of components i. and ii., of        at least one ester, wherein the sum of the weight components i.        and ii. in the organic phase is 100 wt. %,-   II) from 0 to about 50 wt. %, preferably from about 5 wt. % to about    50 wt. %, preferably from about 5 wt. % to about 45 wt. %, more    preferably from about 5 wt. % to about 35 wt. %, more preferably    from about 10 wt. % to about 25 wt. %, based on the total weight of    the composition, of water or aqueous phase,-   III) from 0 to about 60 wt. %, based on the total weight of the    composition, of at least one additive,    wherein the sum of the weight components I) to III) is 100 wt. %.

The drilling composition according to this aspect of the invention ispreferably an oil phase for an emulsion to be used as a drilling fluid,or an emulsion to be used as a drilling fluid, the emulsion beingpreferably a water in oil (W/O) emulsion.

In a preferred form of the organic phase I) according to the invention,component i. comprises at least one synthetic or natural, linear orbranched, cyclic or non-cyclic hydrocarbon, preferably at least onesynthetic or natural, linear or branched, cyclic or non-cyclic alkane,preferably at least one alkane selected from the group consisting ofn-alkanes, i-alkanes, sec-alkanes, tert-alkanes, preferably at least oneC₅ to C₄₀, more preferably at least one C₈ to C₄₀, yet more preferablyat least one C₁₀ to C₃₀, more preferably at least one C₁₀ to C₂₅ alkaneselected from the group consisting of n-alkanes, i-alkanes, sec-alkanes,tert-alkanes, or a mixture of two or more thereof, whereby at least onebranched and/or cyclic alkane is preferred and at least one iso-alkaneis particularly preferred. In a particularly preferred embodiment of theinvention, component i. is a mixture of at least one isoalkane,preferably at least one synthetic isoalkane, and at least one mineraloil, preferably at least one low toxicity or non-toxic mineral oil.Component i., or at least a part thereof, is preferably obtainable by aprocess described in detail in CA 2,265,197 or U.S. Pat. No. 6,410,488B1, whose disclosure in this respect is introduced by reference andforms part of the present disclosure. Component i. according to theinvention can be characterized by its properties. Component i.preferably has a content of aromatic organic compounds of less thanabout 10 wt. %, preferably of less than about 8 wt. %, most preferablyof less than about 6.5 wt. %, with a preferred polynuclear aromaticcontent measured by high resolution mass spectrometry (HRMS) accordingto the United States Environmental Protection Agency (EPA) method ofless than 50 ppm, preferably of less than 40 ppm, more preferably lessthan 30 ppm, yet more preferably less than 20 ppm, most preferably ofless than 10 ppm, whereby wt. % and ppm amounts are based on the totalamount of component i. Component i. preferred according to the inventionalso has low sulphur content, for example less than about 10 ppm, morepreferably less than about 7 ppm, yet more preferably less than about 5ppm, most preferably less than about 3 ppm. Preferred components i. alsohave a viscosity determined according to ASTM D445 at 40° C. of between1 and 10 centistokes, preferably of less than 7 centistokes, morepreferably of less than 5 centistokes, most preferably of between 2centistokes and 4 centistokes, as well as a pour point determinedaccording to ASTM D97 in the range from about −60° C. to about −10° C.,more preferably in the range from about −58° C. to about −15° C. Thepreferred component i. according to the invention also has low toxicityto animals, to marine life, and to humans, as measured by standard testssuch as the mysid shrimp test, and defined by LC₅₀ and/or LD₅₀ values.Preferred components i. are commercially available products with tradenames PureDrill® HT-40, PureDrill® HT30 and PureDrill® IA35 (all fromPetro-Canada, Canada), EDC 95-11 (from Total Fluides, France), andSaraline® 185V (from Shell in Malaysia), whereby PureDrill® HT-40 isparticularly preferred according to the invention.

In a preferred aspect of the organic phase I) according to theinvention, the at least one ester is at least one ester selected fromthe group consisting of esters formed from at least one C₁ to C₂₄monocarboxylic acid with at least one monofunctional alcohol.

The at least one ester of the organic phase I) according to theinvention can be selected from natural and synthetic esters, or mixturesof at least two thereof. By natural esters are understood esters whichthemselves occur naturally, for example esters of plant or animalorigin, as well as esters formed from at least one naturally occurringcarboxylic acid and/or at least one naturally occurring alcohol. The atleast one ester according to the invention preferably has solidificationvalues (pour point and setting point) below −10° C. and more preferablybelow −15° C. The at least one ester according to the invention ispreferably fluid and pumpable at temperatures at least in the range fromabout −10° C. to about 5° C., preferably at temperatures in the rangefrom about 0° C. to about 5° C., as well as above 5° C. At the sametime, particularly for safety reasons, the flash points of these estersare preferably as high as possible, whereby the at least one esterpreferably has a flash point measured according to ASTM D93 above about80° C., preferably above about 100° C., more preferably above about 120°C., yet more preferably above about 150° C., even more preferably aboveabout 160° C. The esters preferred according to the invention alsoadvantageously have viscosity values (measured according to ASTM D2983,using a Brookfield RVT viscometer) at temperatures of 0° C. to 5° C. ofnot more than 50 mPa·s and preferably of at most 45 mPa·s or lower.Esters which are preferred according to the invention are described inDE 39 07 391 A1, DE 39 07 392 A1, DE 38 42 703 A1 and DE 38 42 659 A1,whose disclosure concerning esters is hereby incorporated into thepresent disclosure.

When selecting the appropriate alcohol components for the esters it isrecommended to take account of the following additional considerations:When the ester is used in practice, it is not always possible to excludepartial saponification of the ester. Free alcohols form, in addition tothe free carboxylic acids thus formed or carboxylic acid salts formingtogether with the alkali reserves. They should be selected such thateven after partial hydrolysis operational conditions are ensured whichare ecologically and toxicologically harmless, withinhalation-toxicological considerations in particular being taken intoaccount. The alcohols used for the ester formation preferably inparticular possess such a low volatility that in the free state underconditions to be expected in practice, they do not result in anynuisance on the working platform.

The at least one ester of component ii. of the composition according tothe invention can be described by means of the following sub-classes.

In a first sub-class of the at least one ester of component ii. of thepresent invention, the at least one ester is preferably selected fromC₁-C₅ monocarboxylic acid esters. The esters of C₁-C₅ monocarboxylicacids are reaction products of monofunctional alcohols, i.e. alcoholswith one hydroxy group. In this case the carbon number of the alcohol isat least 6, but is preferably higher, for example at least 8 to 10carbon atoms.

In this sub-class of the at least one ester of component ii. of thecomposition according to the invention the most preferred esters arederived from monocarboxylic acids with 2 to 4 carbon atoms, with aceticacid being particularly preferred as the ester-forming component.

For this sub-class of esters based on very short-chain (C₁-C₅)monocarboxylic acids, it is preferred to use comparatively long-chainmonofunctional alcohols, preferably with up to 24 carbon atoms,preferably with from 6 to 24, more preferably from 8 to 24 carbon atoms,so as to reduce sufficiently the volatility of the ester. It is regardedas particularly preferred that even after partial hydrolysis in use, thedrilling fluids are ecologically and toxicologically harmless,particularly inhalation-toxicologically harmless under workingconditions. In practical use it is assumed that the at least slightlyheated drilling fluid is re-circulated and freed, particularly byscreening, from the drill cuttings it takes up. With progressive ageingand the partial hydrolysis thus caused, problems can arise not only fromthe formation of free fatty acids and their salts, but the freed alcoholcomponents can also cause difficulties in practical operation. Thisalcohol content must always be taken into consideration if alcohol vapornuisance is to be expected as a result of its volatility and therequired operation temperatures.

Suitable alcohols, particularly suitable monofunctional alcohols can beof natural and/or synthetic origin. Straight-chain and/or branchedalcohols can be used here. If monofunctional alcohols of natural and/orsynthetic origin which are predominantly aliphatic saturated are presentin the esters used according to the invention, then such alcohols with 8to 15 carbon atoms are thus preferably used for ester formation. Theirvapor pressure is so low in the operational conditions occurring inpractice that the problem area addressed above does not apply here.Olefin mono- and/or poly-unsaturated alcohols are also suitable, such ascan be obtained, for example, by the selective reduction of naturallyoccurring unsaturated carboxylic acids, for example fatty acids, ortheir esters. The alcohols can, however, also be of synthetic origin.

Esters of monofunctional alcohols are not, however, limited to thiscarbon number range. Higher monofunctional alcohols can also beconsidered, of which the esters with the carboxylic acids of mediumchain length defined according to this embodiment of the invention yieldoils or oil components with usable rheological properties. Particularlyto be considered here are olefin mono- and/or poly-unsaturated alcoholswhich can, for example, have up to 24 carbon atoms or even highernumbers of carbon atoms. Alcohols of this type can be obtained inparticular by the selective reduction of corresponding natural fattyacids.

In a second sub-class of the at least one ester of component ii. of thecomposition according to the invention, the esters, fluid at roomtemperature and having flash points above 80° C., are derived frommonocarboxylic acids of synthetic and/or natural origin with 6 to 11carbon atoms and monofunctional alcohols.

In this embodiment it is also preferred that alcohol components are usedin the esters which even after a partial ester cleavage are ecologicallyand toxicologically harmless in practical use, in particular theinvention takes into account in this regard the inhalation-toxicologicalproblems which can become significant when dealing with the oil-basecomposition in practical use.

In this sub-class of the at least one ester of component ii. of thecomposition according to the invention, the esters are based, on thecarboxylic acid side, on synthetic and/or natural monocarboxylic acidswith 6 to 11 carbon atoms, which can be straight-chain and/or branched.Straight-chain and as a rule even-numbered carboxylic acids in thisrange can be derived particularly from oils or fats of natural originand are known to form the so-called pre-fatty-acids with from 6 to 10carbon atoms. Synthetic carboxylic acids of this type are also easilyobtainable, for example, by the oxidation of Ziegler alcohols. Branched,or mixtures of branched and straight-chain carboxylic acids in thisrange can be obtained from numerous processes in the petrochemicalindustry. Esters of this type preferably contain at least 6 and betterstill at least 7 carbon atoms in the alcohol component. With thiscomparatively high lower limit value for the alcohol component, it ispossible to ensure that in practical use, even after a partial estercleavage, toxicological and particularly inhalation-toxicologicalproblems can be overcome by simple means. Particularly preferredalcohols are those having up to 24 or more carbon atoms and the C₈ toC₁₅ alcohols mentioned above in connection with the first sub-class ofthe at least one ester of component ii. of the composition according tothe invention.

In a third sub-class of the at least one ester of component ii. of thecomposition, these are esters of saturated aliphatic C₁₂-C₁₆monocarboxylic acids and monofunctional C₂-C₁₂, preferably C₄-C₁₂alcohols or mixtures thereof.

The presence of saturated carboxylic acids containing less than 16carbon atoms and, more especially, from 12 to 14 carbon atoms ispreferred in this context. In small quantities, the contents of suchlower, fully saturated fatty acids often present in natural startingmaterials are frequently valuable mixture components. Their esters arenot vulnerable to oxidation under practical in-use conditions and theirrheological properties allow them to replace to a certain extent purehydrocarbon oils in practice.

In one particularly preferred aspect of this sub-class of the at leastone ester of component ii. of the composition of the invention asdescribed above, at least the predominant part, i.e. at least 50%,preferably at least 60%, of the ester used is based on saturatedaliphatic C₁₂-C₁₄ monocarboxylic acids.

The esters used in accordance with this sub-class of the at least oneester of component ii. of the composition of the invention ofmonofunctional alcohols and selected monocarboxylic acids can be derivedfrom either straight chain or branched hydrocarbon chains. Preferred arethe esters of straight chain acids, in particular the esters ofsaturated C₁₂₋₁₆ and more especially C₁₂₋₁₄ monocarboxylic acids andmonofunctional alcohols having the C chain lengths defined in accordancewith this sub-class of the at least one ester of component ii. of thecomposition of the invention. These can form esters which show adequaterheological properties, even down to temperatures in the range of from 0to 5° C., and in particular are flowable and pumpable in thattemperature range. In the context of this sub-class of the at least oneester of component ii. of the composition of the invention, preferredesters are saturated compounds which have a Brookfield (RVT) viscosity,measured as described above, at a temperature of 0° C. to 5° C., of nomore than 50 mPa·s and preferably of no more than 40 mPa·s. By selectingsuitable components for the ester-forming reaction, it is possible toadjust the viscosity at temperatures in the above-mentioned range tovalues of at most 30 mPa·s, for example in the range of from 10 to 20mPa·s. It is clear that this affords important advantages for offshoredrilling where the surrounding water can have very low temperatures.

The alcohol components of the esters or ester mixtures according to thisembodiment of the invention are preferably derived from straight-chainand/or branched-chain saturated alcohols, preferably alcohols containingat least 3 carbon atoms and, more especially, to alcohols containing upto about 10 carbon atoms, whereby alcohols with 4, 5, 6, 7, 8, or 9carbon atoms can also be used. The alcohols can also be of naturalorigin, in which case they have normally been obtained from thecorresponding carboxylic acids or their esters by hydrogenatingreduction. However, the invention is by no means limited to startingmaterials of natural origin. Both on the monoalcohol side and on themonocarboxylic acid side, the starting materials of natural origin maybe partly or completely replaced by corresponding components ofsynthetic origin. Typical examples of alcohols are the corresponding oxoalcohols (branched alcohols) and the linear alcohols obtained by theZiegler process. Similarly, monocarboxylic acid components present inparticular in carboxylic acid mixtures can be derived from petrochemicalsynthesis.

In a preferred embodiment, the esters used in accordance with thisaspect of the composition according to the invention based on selectedindividual components or on ester mixtures have solidification values(pour point and setting point) below −10° C. and more especially below−15° C. Despite this high mobility at low temperatures, the molecularsize of the ester in accordance with the invention ensures that theflash points of the esters are sufficiently high, being at least 80° C.,but generally exceeding a temperature limit of about 100° C. Estershaving flash points above 150° C. to 160° C. are preferred. It ispossible to produce esters of the described types which have flashpoints of 185° C. or higher.

In another preferred aspect of this third sub-class of the at least oneester of composition ii. according to the invention, the esters of therange required in accordance with the invention for the saturated C₁₂₋₁₆monocarboxylic acids are derived from materials of predominantlyvegetable origin. Carboxylic acids or carboxylic acid mixturespredominantly containing saturated monocarboxylic acids within thestated range can be obtained, for example, from renewable triglycerides,such as coconut oil, palm kernel oil and/or babassu oil. Fatty acidmixtures of this origin normally contain a limited quantity of lowerfatty acids (C₆₋₁₀) of generally at most about 15%. Their content ofC₁₂₋₁₄ acids is by far predominant, generally making up at least 50% andnormally 60% or more of the carboxylic acid mixture. The small remainderconsists of higher fatty acids, with unsaturated components playing aconsiderable role. Accordingly, carboxylic acid mixtures of this type,by virtue of their natural structure, readily lead to materials havingsatisfactory rheological properties.

In a fourth sub-class of the at least one ester of component ii. of thecomposition according to the invention these can be esters ofmonofunctional C₂-C₁₂ alcohols (alkanols) and olefinically mono- and/orpolyunsaturated C₁₆-C₂₄ monocarboxylic acids or mixtures thereof withsmall quantities of other, more especially saturated monocarboxylicacids.

The esters according to this embodiment may be assigned to the class ofreaction products of monofunctional carboxylic acids, preferably C₁₆-C₂₄carboxylic acids, with monofunctional alcohols. The carboxylic acids maybe derived from unbranched or branched hydrocarbon chains, preferablylinear chains. Monocarboxylic acids of this type and of the C₁₆-C₂₄range and esters thereof are unsuitable as predominantly saturatedhydrocarbon compounds due to their comparatively high solidificationpoints. Even then, however, esters of this type are flowable andpumpable down to temperatures of 0° C. to 5° C. providing an adequatelevel of olefinically unsaturated ester constituents is provided. Inthis sub-class of the at least one ester of component ii. of thecomposition of the invention, therefore, esters of the described type ofwhich more than 70% by weight and preferably more than 80% by weight arederived from olefinically unsaturated C₁₆-C₂₄ carboxylic acids arepreferably used. Preferred natural starting materials are carboxylicacid mixtures which contain at least 90% by weight olefinicallyunsaturated carboxylic acids in the above C range. The unsaturatedcarboxylic acids may be mono- and/or polyolefinically unsaturated. Wherecarboxylic acids or carboxylic acid mixtures of natural origin are used,the double ethylenic double bond in particular and, to a lesser extent,even a triple ethylenic double bond per carboxylic acid molecule plays arole in addition to a single ethylenic double bond in the molecule.Particulars of this are given in the following.

In conjunction with the choice of esters of monofunctional reactants inaccordance with the fourth sub-class of the at least one ester ofcomponent ii. of the composition of the invention, the choice of such acomparatively highly unsaturated carboxylic acid component in the estersensures that the esters, and invert emulsions comprising them, show therheological properties required in practice, particularly at relativelylow temperatures. The comparatively highly unsaturated esters containing16 to 24 carbon atoms in the monocarboxylic acid component, which areused in accordance with this embodiment of the invention, havesolidification points (pour point according to ASTM D97 and settingpoint) below −10° C. and more especially below −15° C. Despite this highmobility at low temperatures, the molecular size of the ester prescribedin accordance with this aspect of the invention ensures that theflashpoints of the esters are sufficiently high, being at least 80° C.,and generally exceeding a temperature limit of approximately 100° C.Esters having flashpoints above 160° C. are preferred. Esters of thedescribed type showing high mobility, even at low temperatures, andhaving flashpoints of 185° C. or higher can be produced withoutdifficulty by processes known to the skilled person.

In conjunction with these high flashpoints determined by the size of themolecule, it is possible at the same time to ensure that the viscosityvalues are within the required limits. Thus, preferred esters of thetype described for this embodiment according to the invention show aviscosity (measured with a Brookfield RVT viscometer as above) at atemperature of 0° C. to 5° C. of not more than 55 mPa·s and preferablyof at most 45 mPa·s or lower. It is possible to adjust values of 30 oreven higher, for example in the range of from 20 to 25 mPa·s, attemperatures in the range indicated.

Among the unsaturated esters suitable for use in accordance with thisfourth sub-class of the at least one ester of component ii. of thecomposition of the invention, there are two preferred types of ester.

The first of these preferred types of ester is based on unsaturatedC₁₆-C₂₄ monocarboxylic acids of which no more than about 35% by weightare diolefinically and, optionally, polyolefinically unsaturated. Intheir case, therefore, the content of di-and polyunsaturated carboxylicacid residues in the ester is comparatively limited. Within thissub-class it is preferred that at least about 60% by weight of thecarboxylic acid residues are monoolefinically unsaturated.

The second preferred type of ester is derived from C₁₆-C₂₄ unsaturatedmonocarboxylic acid mixtures of which more than 45% by weight andpreferably more than 55% by weight are derived from diolefinicallyand/or polyolefinically unsaturated acids within the above C range.

Preferred monoethylenically unsaturated carboxylic acids within theabove carbon range are hexadecenoic acids (palmitoleic acid (C₁₆)),oleic acid (C₁₈), the related ricinoleic acid (C₁₈) and erucic acid(C₂₂). A preferred di-unsaturated carboxylic acid within the range inquestion here is linoleic acid (C₁₈) while a preferred triethylenicallyunsaturated carboxylic acid is linolenic acid (C₁₈).

Selected individual esters formed from an unsaturated monocarboxylicacid and a monoalcohol can be used as the ester in accordance with thisfourth sub-class of the at least one ester of component ii. of thecomposition of the invention. One example of such esters is given by theesters of oleic acid, for example of the oleic acid isobutyl ester type.So far as the rheology of the system is concerned and/or for reasons ofavailability, it is frequently desirable to use esters from acidmixtures. This is preferred so far as meeting the preferredspecifications of the esters according to this aspect of the inventionis concerned. This can also be preferred for all embodiments of theester in the composition according to the invention, not only for thissub-class.

As already mentioned, the first of these two types is distinguished bythe fact that its content of di-unsaturated and polyunsaturated acids islimited and does not exceed about 35% by weight. Vegetable oils ofnatural origin, of which the hydrolysis or transesterification givesmixtures of carboxylic acids or carboxylic acid esters of the typerequired here, are for example palm oil, peanut oil, castor oil and, inparticular, rapeseed oil. Suitable rapeseed oils are both traditionaltypes of high erucic acid content and also the more modern types ofreduced erucic acid content and increased oleic acid content.

Esters of the first type according to this sub-class of the at least oneester of component ii. of the composition according to the inventionwhich correspond to this definition have the advantage that problemspossibly arising from the lack of stability to oxidation are reduced. Inpractice, the drilling composition is continuously pump-circulated and,in the process, is brought constantly into contact with atmosphericoxygen, often over a large area and at least slightly elevatedtemperatures, for the purpose of separating out the rock cuttingsbrought up, for example by sieving.

However, carboxylic acid mixtures of the second type mentioned inconnection with this fourth sub-class of the at least one ester ofcomponent ii. of the composition of the invention are also of practicalsignificance for use in accordance with the invention. This isattributable in part to their broad accessibility from natural fats ofanimal and/or vegetable origin. Examples of oils which have a highcontent of C₁₆₋₁₈ or C₁₆₋₂₂ carboxylic acids and which, at the sametime, contain at least about 45% of at least diethylenically unsaturatedcarboxylic acids are cottonseed oil, soybean oil, sunflower oil andlinseed oil. The tall oil acids isolated during the recovery ofcellulose also fall within this range. However, starting materials ofthe last type are generally distinguished by more or less largeadditional contents of resin constituents. A typical animal startingmaterial for the production of corresponding carboxylic acid mixtures isfish oil, particularly herring oil.

The alcohol components of the esters or ester mixtures according to thisfourth aspect of the composition ii. of the invention are preferablyderived from straight chain and/or branched-chain saturated alcohols,preferably alcohols containing at least four carbon atoms and, morepreferably alcohols containing up to about ten carbon atoms, asdescribed above. The alcohols can also be of natural origin, in whichcase they have normally been obtained from the corresponding carboxylicacids or their esters by hydrogenating reduction, or they can be ofsynthetic origin.

Esters which are particularly preferred according to the invention arebased on C₈-C₁₄ fatty acids or difatty acids thereof, or on C₈-C₁₀ orC₁₂-C₁₄ fatty acids or difatty acids thereof, of which C₈-C₁₄ fattyacids or C₁₂-C₁₄ fatty acids are preferred. Particularly preferredesters are based on C₈ to C₁₄, C₈ to C₁₀ and/or C₁₂ to C₁₄ fatty acids,esterified with a branched alcohol, preferably with a branched C₄ to C₁₂alcohol, yet more preferably with a branched C₆-C₁₀ alcohol, yet morepreferably with a branched C₇-C₉ alcohol, more preferably with anethylpentyl alcohol, a propylpentyl alcohol, an ethylhexyl alcohol, apropylhexyl alcohol, an ethylheptyl alcohol, a propylheptyl alcohol,more preferably with an ethylhexyl alcohol, preferably with 2-ethylhexylalcohol or with 3-ethylhexyl alcohol, most particularly preferably with2-ethylhexyl alcohol. So far as the rheology of the system is concernedand/or for reasons of availability, it is frequently desirable to useesters from acid mixtures.

In a preferred embodiment, the at least one ester has a carbon chaindistribution of the acid-derived component determined by gaschromatography (GC) according to ISO 5508 with carbon numbers in theranges of from 0 to 2.00%, preferably in the range of from 0 to 1.00%,more preferably in the range of from 0 to 0.5% C₆, in the range of from3.00% to 10.00%, preferably in the range of from 3.00 to 8.00%, morepreferably in the range of from 4.00 to 7.00% C₈, in the range of from3.00% to 10.00%, preferably in the range of from 3.00 to 9.00%, morepreferably in the range of from 5.00 to 8.00% C₁₀, in the range of from50.00% to 94.00%, preferably in the range of from 55.00 to 90.00%, morepreferably in the range of from 60.00 to 85.00% C₁₂, in the range offrom 0 to 25.00%, preferably in the range of from 5.00 to 20.00%, morepreferably in the range of from 10.00 to 20.00% C₁₄, in the range offrom 0 to 5.00%, preferably in the range of from 1.00 to 4.00%, morepreferably in the range of from 2.00 to 4.00% C₁₆ and in the range offrom 0 to 1.00%, preferably in the range of from 0.01 to 0.90%, morepreferably in the range of from 0.1 to 0.6% C₁₈. The acid-derivedcomponent determined by gas chromatography of an ester refers to thechromatographic equivalent of an acid, which would have been formed uponhydrolytic cleavage of that ester into an alcohol and an acid.

In another preferred embodiment, the at least one ester has a carbonchain distribution of the acid-derived component determined by gaschromatography (GC) according to ISO 5508 with carbon numbers in therange of from 0 to 2.00%, preferably in the range of from 0 to 1.00%,more preferably in the range of from 0 to 0.5% C₆, in the range of from0 to 10.00%, preferably in the range of from 1.00 to 7.00%, morepreferably in the range of from 2.00 to 5.00% C₈, in the range of from 0to 10.00%, preferably in the range of from 1.00 to 7.00%, morepreferably in the range of from 2.00 to 5.00% C₁₀, in the range of from50.00% to 95.00%, preferably in the range of from 60.00 to 90.00%, morepreferably in the range of from 65.00 to 85.00% C₁₂, in the range offrom 5.00% to 35.00%, preferably in the range of from 8.00 to 30.00%,more preferably in the range of from 10.00 to 25.00% C₁₄, in the rangeof from 0 to 5.00%, preferably in the range of from 1.00 to 4.00%, morepreferably in the range of from 2.00 to 4.00% C₁₆ and in the range offrom 0 to 1.00%, preferably in the range of from 0.01 to 0.90%, morepreferably in the range of from 0.1 to 0.6% C₁₈. The acid-derivedcomponent determined by gas chromatography of an ester refers to thechromatographic equivalent of an acid, which would have been formed uponhydrolytic cleavage of that ester into an alcohol and an acid.

The at least one ester used as component ii. of the compositionaccording to the invention preferably has at least one, preferably atleast two, more preferably at least three, yet more preferably at leastfour, more preferably at least five, more preferably all of thefollowing properties, in any combination with each other:

-   α1) a viscosity determined according to ASTM D2983 using a    Brookfield RVT viscometer (Brookfield, RVT viscosity) at    temperatures of 0° C. to 5° C. of not more than 50 mPa·s, preferably    of not more than 10 mPa·s and preferably in the range of from about    2.0 to 5.0 mPa·s, more preferably in the range of from about 2.5 to    4.5 mPa·s, yet more preferably in the range of from about 2.7 to 4.0    mPa·s;-   α2) an acid value determined according to ISO 660 in a range of from    0 to 2.0 mg KOH/g, preferably in a range of from 0.001 to 1.8 mg    KOH/g, preferably in a range of from 0.01 to 1.5 mg KOH/g,    preferably in a range of from 0.05 to 1.0 mg KOH/g;-   α3) a hydroxyl value determined according to DIN 53240 in a range    from 0 to 1.5 mg KOH/g, preferably in a range from 0 to 1.0 mg    KOH/g, more preferably in a range from 0 to 0.8 mg KOH/g;-   α4) biodegradability in seawater measured according to OECD    Guideline for Testing of Chemicals, No. 306, adopted 17 Jul. 1992,    in the range of from 90% to 100%, preferably in the range of from    92% to 100%, more preferably in the range of from 95% to 100%;-   α5) non-toxicity measured by the 96 hour LC₅₀ Mysid shrimp acute    toxicity bioassay test result of greater than 800,000, preferably of    greater than 900,000, more preferably of greater than 1,000,000 and    most preferably of greater than 1,100,000.-   α6) a flashpoint measured according to ASTM D93 of above 150° C.,    more preferably of above 160° C., even more preferably of above 170°    C., yet more preferably above 175° C., more preferably in a range    from 175° C. to 200° C., even more preferably in a range from    177° C. to 182° C.

It is also possible according to a further embodiment of the compositionaccording to the invention that the at least one ester is a mixture ofat least two esters selected from any of the esters described above.

The composition as preferred according to the invention can compriseonly or predominantly starting materials of natural origin, but is by nomeans limited to starting materials of natural origin. Both on thealcohol side and on the carboxylic acid side, the starting materials maybe of natural origin or may be partly or completely of synthetic origin.Starting materials of natural origin are advantageous in their provenlower toxicological values, their ready degradability and their readyaccessibility. The ultimately desired destruction, preferably naturaldestruction, of the used composition is favored if esters of the typedescribed herein are both aerobically and anaerobically degradable.

The water or aqueous phase according to component II) of the compositionaccording to the invention is preferably a salt solution, preferably asaturated salt solution, preferably a saturated solution of CaCl₂ and/orKCl.

Multi-substance mixtures further comprising one or more additives alsofall within the framework of the invention. In principle, any mixturescan be used provided that they fulfill the basic rheologicalrequirements for drilling fluids, in particular for invert-drillingfluids.

Additives according to the invention can be any additives which arecommonly used in drilling compositions and which are known to theskilled person. In a preferred aspect of the composition according tothe invention, the at least one additive is at least one additiveselected from the group consisting of weighting agents, fluid lossadditives, pH modifiers such as, for example, alkali reserves, viscositymodifiers, filtration control agents, emulsifiers, salts, wettingagents, dispersants.

Weighting agents suitable for use in drilling compositions are wellknown to the skilled person. Weighting agents suitable according to theinvention are preferably water-insoluble weighting agents such asbarite, calcite, mullite, galena, hematite, manganese oxides, ironoxides, or combinations of these, or water-soluble weighting agents suchas water soluble salts of zinc, iron, barium, calcium or combinations ofthese and similar compounds. Further examples of suitable weightingagents are Fe₂O₃, MnO₄ and CaCO₃. The weighting agent preferredaccording to the invention to establish the necessary pressureequalization is barite, which comprises predominantly barium sulphate,which is added in quantities adapted to the particular conditions to beexpected in the well. For example, it is possible by addition of bariteto increase the specific gravity of the drilling mud to values of up to2.5 and preferably in the range of from 1.3 to 1.6.

Fluid loss additives can be used in embodiments of the compositionaccording to the invention. In a preferred embodiment according to theinvention, organophilic lignite is used as a fluid loss additive and,hence, for forming an impervious coating in the form of a substantiallyliquid-impermeable film over the walls of the well. Suitable quantitiesare, for example, in the range of from 15 to 20 lb/bbl or in the rangeof from 20 to 60% by weight, preferably in a range of from 30 to 50% byweight, based on the ester phase.

Use may also be made according to the invention of agents which modifythe pH of the composition: Examples are given in EP 382 070 A1. Theteaching of this earlier application is based on the concept of using afurther additive in ester-based invert drilling fluids, which is suitedto keeping the desired rheological data of the drilling fluid in therequired range even when, in use, increasingly large amounts of freecarboxylic acids are formed by partial ester hydrolysis. These liberatedcarboxylic acids should not only be trapped in a harmless form, itshould moreover be possible to reform these free carboxylic acids,preferably into valuable components with stabilizing or emulsifyingproperties for the whole system. According to this teaching, alkalineamine compounds of marked oleophilic nature and at best limited watersolubility, which are capable of forming salts with carboxylic acids,can be used as additives in the oil phase. The oleophilic aminecompounds can at the same time be used at least in part as alkalireserves in the invert drilling fluid, they can however also be used incombination with conventional alkali reserves, particularly togetherwith lime. The use of oleophilic amine compounds which are at leastlargely free from aromatic constituents is preferred. In particular,optionally olefin unsaturated aliphatic, cycloaliphatic and/orheterocyclic oleophilic basic amine compounds, can be considered, whichcontain one or more N-groups capable of forming salts with carboxylicacids. In a preferred embodiment the water-solubility of these aminecompounds at room temperature is at most about 5% by weight and is mostpreferably below 1% by weight.

Typical examples of such amine compounds are primary, secondary and/ortertiary amines, which are at least predominantly water-insoluble, andwhich can also to a limited extent be alkoxylated and/or substitutedparticularly with hydroxyl groups. Further examples are correspondingaminoamides and/or heterocycles containing nitrogen as ring constituent.For example, basic amine compounds are suitable which have at least onelong-chain hydrocarbon radical with preferably 8 to 36 carbon atoms,particularly with 10 to 24 carbon atoms, which can also be olefin mono-or poly-unsaturated. The oleophilic basic amine compounds can be addedto the drilling fluid in amounts of up to about 10 lb/bbl, preferably inamounts up to about 5 lb/bbl and particularly in the range of about 0.1to 2 lb/bbl. It has emerged that the use of such oleophilic basic aminecompounds can effectively prevent thickening of the mud system, whichhas previously been attributed to a disturbance in the W/O invert systemand also to the formation of free carboxylic acids by ester hydrolysis.

One preferred limitation is associated with the use of the estersaccording to the third and fourth embodiments in invert oil drillingfluids of the type used in the present invention. This limitation arisesout of the difficulty that, in principle, the carboxylic acid esters arevulnerable to hydrolysis.

It is preferred in all embodiments, but particularly in the third andfourth embodiments that strong hydrophilic bases of inorganic and/ororganic nature, such as alkali metal hydroxides or strongly hydrophilicamines such as diethanolamine and/or triethanolamine, are not used insignificant quantities as alkali reserve. Lime (calcium hydroxide) isoften added as the alkali reserve, more especially for protectionagainst inrushes of acidic gases such as CO₂ and/or H₂S into thedrilling fluid and hence for protection against corrosion. An additionof lime such as this may be used as the alkali reserve in accordancewith the invention. However, it is preferred to ensure that onlycomparatively small quantities of this alkaline component areincorporated. In a preferred embodiment of the invention, the maximumaddition of lime is of the order of 2 lb/bbl (lime/drillingcomposition), and it may be preferred to work with lime contents in thedrilling mud slightly below this, e.g., therefore from about 0.5 toabout 1.8 lb/bbl (lime/drilling fluid). Other known alkali reserves canbe used in addition to or in place of the lime. The less basic metaloxides, such as zinc oxide, should particularly be mentioned here. Evenwhen these acid traps are used, care is still taken that the amountsused are not too large, so as to prevent undesired premature ageing ofthe drilling fluid, associated with an increase in viscosity andtherefore a deterioration in the rheological properties. The specialfeatures discussed here of the process according to the inventionprevent, or at least restrict, the formation of undesirable amounts ofhighly active O/W emulsifiers, so that the good rheological propertiesare maintained for a sufficiently long time in use even when there isthermal ageing.

Viscosity modifiers suitable for use in drilling compositions are wellknown to the skilled person. Viscosity modifiers can be viscosifiers(also known as structure building agents or thickeners) which increaseviscosity, or deflocculants which decrease viscosity, whereby in thepresent invention viscosifiers are preferred. Viscosifiers can beselected from organic or inorganic thickeners, for example, xanthan gum,guar gum, glycol, carboxymethylcellulose, polyanionic cellulose orstarch. Deflocculants can be selected from anionic polyelectrolytes suchas acrylates, polyphosphates, lignosulfonates or tannic acid derivativessuch as Quebracho. A viscosifier preferred according to the invention isa cation-modified finely particulate bentonite, which can be usedparticularly in amounts of about 8 to 10 lb/bbl (pounds per barrel) orfrom about 1 to about 60 wt. %, preferably from about 2 to about 55% byweight, based on the total weight of the composition.

The emulsifiers which can be used in practice according to the inventionare systems which are capable of forming water in oil (W/O) emulsions.In particular, selected oleophilic fatty acids or salts thereof, forexample, those based on amidoamine compounds, in particular polyaminatedfatty acids, can be considered. Examples of these are described in U.S.Pat. No. 4,374,737 and the literature cited therein. Particularlypreferred emulsifiers are reaction products of a polyamine with a fattyacid or fatty acid anhydride to give a fatty amide, which issubsequently reacted with an anhydride, preferably maleic acidanhydride, acrylic acid anhydride or fumaric acid anhydride, mostpreferably maleic acid anhydride, in the presence of at least onecrosslinker. Examples of these are described in U.S. Pat. No. 4,658,036and the literature cited therein, whose disclosures are herebyincorporated by reference. A particularly suitable type of emulsifier isthe product sold by Halliburton (Baroid Fluid Services) under the brandname “EZ-MUL®”.

Emulsifiers of the type in question are sold commercially as highlyconcentrated active-substance preparations and in one embodiment can,for example, be used in amounts of about 20 to 80% by weight,particularly in amounts of about 30 to 70% by weight, based on theorganic phase. It is, however, preferred that emulsifiers are used inamounts in the range from about 0.5 wt. % to about 15 wt. %, preferablyin amounts in the range from about 0.5 wt. % to about 10 wt. %, morepreferably in amounts in the range from about 1 wt. % to about 8 wt. %,more preferably in amounts in the range from about 1 wt. % to about 6wt. %, based on the organic phase.

The aforementioned emulsifiers or emulsifier systems can optionally alsobe used to improve the oil wetability of the inorganic weightingmaterials. In addition to the aminoamides already discussed, alkylbenzenesulfonates and imidazoline compounds are further examples.Additional information regarding these and also regarding the relevantprior art can be found in the following publications: GB 2 158 437, EP229 912 and DE 32 47 123, whose disclosures are hereby incorporated byreference.

The at least one salt is preferably selected from the group consistingof metal halides, particularly preferably alkali metal or alkaline earthmetal halides. The dispersed aqueous phase in the composition accordingto the invention, which is preferably in the form of an invert drillingfluid, is preferably loaded with soluble salts. Calcium chloride and/orpotassium chloride are preferably used here, and saturation of theaqueous phase with the soluble salt at room temperature is preferred.

In the aspect of the composition according to the invention comprisingwater or aqueous phase, the composition is preferably in the form of anemulsion, preferably in the form of a nanoemulsion or a microemulsion,preferably in the form of a water-in-oil emulsion with number averagedroplet sizes smaller than 1000 μm, preferably in the range from about 5nm to about 1000 μm, preferably in the range from 10 nm to 850 μm, morepreferably in the range from 20 nm to 700 μm, more preferably in therange from 50 nm to 500 μm. The terms “microemulsion” and “nanoemulsion”according to the invention are used to refer to emulsions with dropletsizes in the micrometer and nanometer ranges respectively, whereby thereis a certain amount of overlap between the two ranges and thus the twoterms. According to some definitions in the prior art, microemulsionsare generally considered to form spontaneously on combination of theemulsion components, whereas the formation of nanoemulsions is generallyconsidered to require input of energy, for example in the form ofhomogenization, in particular high pressure homogenization.

The drilling composition according to the invention preferably has atleast one, preferably at least two, more preferably at least three ofthe following properties:

-   β1) a plastic viscosity (PV) measured at 50° C. according to the    herein described test method in the range from 15 to 75 mPa·s,    preferably in a range of from about 15 to about 60 mPa·s, more    preferably in a range of from about 15 to about 40 mPa·s, more    preferably in a range of from about 15 to about 30 mPa·s, yet more    preferably in a range of from about 15 to about 25 mPa·s;-   β2) a yield point (YP) measured at 50° C. according to the herein    described test method in the range from 5 to 45 lb/100 ft² (about    2.4 to about 21.6 Pa), preferably in a range of from about 5 to    about 40 lb/100 ft² (about 2.4 to about 20 Pa), preferably in a    range of from about 6 to about 25 lb/100 ft², (about 2.9 to about 12    Pa), more preferably in a range of from about 8 to about 20 lb/100    ft², (about 3.8 to about 10 Pa);-   β3) a gel strength (GS) measured at 50° C. according to the herein    described test method in the range from 4 to 25 lb/100 ft² (1.9 to    12 Pa), preferably in a range of from about 4 to about 15 lb/100 ft²    (about 1.9 to about 7.2 Pa), preferably in a range of from about 4    to about 10 lb/100 ft², (about 1.9 to about 4.8 Pa), more preferably    in a range of from about 4 to about 8 lb/100 ft², (about 1.9 to    about 3.8 Pa);-   β4) viscosity values (measured according to ASTM D2983, using a    Brookfield RVT viscometer) at temperatures of 0° C. to 5° C. of not    more than 50 mPa·s, preferably of not more than 15 mPa·s and    preferably in the range of from about 2.0 to 5.0 mPa·s, more    preferably in the range of from about 2.5 to 4.5 mPa·s, yet more    preferably in the range of from about 2.7 to 4.0 mPa·s;-   β5) storage stability at 20° C. of at least two weeks, preferably of    at least one month, more preferably of at least three months, more    preferably of at least six months, more preferably of at least one    year,    whereby the combinations of properties β1)β2), β1)β3), β2)β3),    β1)β2)β3), β1)β2)β3)β4), β1)β2)β3)β5), β1)β2)β3)β4)β5), are    preferred, whereby the property combinations β1)β2)β3),    β1)β2)β3)β4), β1)β2)β3)β5) and β1)β2)β3)β4)β35), are particularly    preferred.

One application for the drilling compositions according to the inventionis in offshore drilling for the development of oil and/or gas sources,to provide technically useful drilling fluids of good ecologicalcompatibility. The use of the new drilling fluids is, however, notlimited to the offshore sector. The new drilling fluids can also be usedquite generally for land-supported drilling, including for examplegeothermal drilling, water drilling, geoscientific drilling and minedrilling. In this case, too, the ester-comprising drilling compositionsin accordance with the invention simplify ecotoxic problems. Thedrilling compositions according to the invention exhibit a goodsolubility of organic and inorganic components. In addition, thedrilling compositions based in accordance with the invention on theco-use of esters of the described type are further distinguished byimproved storage stability, improved lubricity and good rheologicalproperties.

A contribution to solving the above problems is also made by a processfor preparation of a drilling composition, comprising the steps:

-   a) providing as component i. from about 20 wt. % to about 99.999 wt.    %, preferably from about 40 wt. % to about 99.990 wt. %, preferably    from about 60 wt. % to about 99.900 wt. %, preferably from about 70    wt. % to about 99 wt. %, more preferably from about 80 wt. % to    about 98.5 wt. %, yet more preferably from about 85 wt. % to about    98 wt. %, even more preferably from about 90 wt. % to about 98 wt.    %, more preferably from about 92 wt. % to about 97 wt. %, most    preferably from about 93 wt. % to about 96 wt. %, based on the total    weight of components i. and ii., of at least one linear or branched,    cyclic or non-cyclic, saturated hydrocarbon,-   b) providing as component ii. from about 0.001 wt. % to about 25 wt.    %, preferably from about 0.5 wt. % to about 20 wt. %, more    preferably from about 1 wt. % to about 15 wt. %, yet more preferably    from about 2 wt. % to about 10 wt. %, even more preferably from    about 2 wt. % to about 8 wt. %, more preferably from about 3 wt. %    to about 7 wt. %, most preferably from about 4 wt. % to about 7 wt.    %, based on the total weight of components i. and ii., of at least    one linear or branched, cyclic or non-cyclic, saturated hydrocarbon,    wherein the sum of the weight amounts provided in a) and b) is 100    wt. %,-   c) combining the at least one hydrocarbon and the at least one    ester.

A contribution to solving the above problems is also made by a processfor preparation of a drilling composition, comprising the steps:

-   A) preparation of an organic phase comprising components    -   i. from about 20 wt. % to about 99.999 wt. %, preferably from        about 40 wt. % to about 99.990 wt. %, preferably from about 60        wt. % to about 99.900 wt. %, preferably from about 70 wt. % to        about 99 wt. %, more preferably from about 80 wt. % to about        98.5 wt. %, yet more preferably from about 85 wt. % to about 98        wt. %, even more preferably from about 90 wt. % to about 98 wt.        %, more preferably from about 92 wt. % to about 97 wt. %, most        preferably from about 93 wt. % to about 96 wt. %, based on the        total weight of components i. and ii., of at least one linear or        branched, cyclic or non-cyclic, saturated hydrocarbon,    -   ii. from about 0.001 wt. % to about 25 wt. %, preferably from        about 0.5 wt. % to about 20 wt. %, more preferably from about 1        wt. % to about 15 wt. %, yet more preferably from about 2 wt. %        to about 10 wt. %, even more preferably from about 2 wt. % to        about 8 wt. %, more preferably from about 3 wt. % to about 7 wt.        %, most preferably from about 4 wt. % to about 7 wt. %, based on        the total weight of components i. and ii., of at least one        ester,-   B) preparation of an aqueous phase comprising from about 50 wt. % to    100 wt. %, preferably from about 55 wt. % to about 99 wt. %, more    preferably from about 70 wt. % to about 95 wt. % water, based on the    total amount of aqueous phase,-   C) combination of the organic phase prepared in step A) with from 0    to about 50 wt. %, preferably from about 5 wt. % to about 50 wt. %,    preferably from about 5 wt. % to about 45 wt. %, more preferably    from about 5 wt. % to about 35 wt. %, more preferably from about 10    wt. % to about 25 wt. %, based on the total weight of the    composition, of the aqueous phase prepared in step B), and-   D) combination of at least one of the organic phase, the aqueous    phase and the combination of the oil phase and the aqueous phase    with from 0 to about 60 wt. %, based on the total weight of    composition, of at least one additive.

The at least one linear or branched, cyclic or non-cyclic, saturatedhydrocarbon is preferably selected from the hydrocarbons mentioned abovein connection with the composition according to the invention.

The at least one ester is preferably at least one ester selected fromthe esters described above in connection with the composition accordingto the invention, preferably from the group consisting of esters formedfrom at least one C₁ to C₂₄ monocarboxylic acid with at least onemonofunctional alcohol.

The aqueous phase is preferably a salt-saturated aqueous phase asdescribed above in connection with the composition according to theinvention.

The at least one additive is preferably at least one additive selectedfrom the additives mentioned above in connection with the compositionaccording to the invention.

The amounts of each of the above components are preferably selected asdescribed above for the composition according to the invention.

The combination in step C) can occur by adding the organic phase to theaqueous phase, by adding the aqueous phase to the organic phase, or byintroducing the organic phase and the aqueous phase at substantially thesame time into a vessel in which they are to be combined. Thecombination preferably occurs with input of energy, preferably in theform of mixing or stirring, preferably rapid stirring, preferablystirring at a rate above 50 rpm, preferably in the range from about 100rpm to about 500 rpm, more preferably in the range from about 200 rpm toabout 450 rpm. The combination can occur at decreased, ambient orelevated temperature, depending on factors such as the components to becombined, the location at which they are combined (for example, indoorsor outdoors), and the desired emulsion droplet size. A combination atambient temperature is preferred.

The at least one additive can be introduced before, during or after anyor all of steps A), B) and C). If one or more additives are introducedin step C), this additive may be introduced at substantially the sametime as combining the organic phase with the aqueous phase as describedabove, or it may be added to either the organic phase or the aqueousphase or to both, for example with at least one additive being added tothe organic phase and at least one further additive being added to theaqueous phase, before combination in step C), or the at least oneadditive may be added to the composition obtained after combination ofthe organic phase with the aqueous phase in step C).

In a variant of the process according to the invention, the at least oneester according to the invention can be added to an already existingdrilling composition comprising at least one hydrocarbon, aqueous phaseand at least one additive, in a so-called post-treatment step. In thiscase it is conceivable that the already existing drilling compositionhas already been used at least once in a drilling operation, prior tothe post-treatment with the at least one ester. It is also possible thatthe already existing drilling composition has not yet been used in adrilling operation before the post-treatment.

The process according to the invention preferably further comprises thestep

-   E) homogenization.

The homogenization is preferably a homogenization of the compositionobtained in step C) or step D) of the process according to theinvention. It is also possible that steps C) and E), or steps C), D) andE) are combined with each other, so that the combination of the oilphase and the aqueous phase with each other and/or with any additiveused takes the form of a homogenization. It is preferred in the processaccording to the invention that the homogenization occurs during orafter at least one of steps C) and D). The homogenization is preferablycarried out at temperatures in the range from 0 to 100° C., preferablyin the range from 5 to 80° C., more preferably in the range from 10 to60° C., yet more preferably in the range from 20 to 50° C., mostpreferably at ambient temperatures. The homogenization may also be ahigh pressure homogenization carried out at pressures in the range from1×10⁷ Pa to 18×10⁷ Pa, preferably in the range from 3×10⁷ Pa to 18×10⁷Pa, more preferably in the range from 5×10⁷ Pa to 15×10⁷ Pa.

It is preferred in the process according to the invention that thecomposition at the end of at least one of steps C), D) and E) is in theform of an emulsion. Thus, an emulsion may be formed by combining theoil phase with the aqueous phase as described for step C) above,optionally in the presence of at least one additive, which may be, forexample, at least one emulsifier. Alternatively, an emulsion may beformed by subjecting the oil phase and the aqueous phase together,optionally in the presence of at least one additive, which may be, forexample, at least one emulsifier, to a homogenization step, as describedfor step E) above. Homogenization, in particular high pressurehomogenization, generally results in emulsions with smaller dropletsizes compared to simple combination of the oil phase and the aqueousphase.

In a preferred embodiment of the process according to the invention, theemulsion is a nanoemulsion or a microemulsion as described above inconnection with the composition according to the invention, with numberaverage droplet sizes smaller than 1000 μm, preferably in the range from5 nm to 1000 μm, preferably in the range from 10 nm to 850 μm, morepreferably in the range from 20 nm to 700 μm, more preferably in therange from 50 nm to 500 μm.

In a preferred aspect of the process according to the invention, the atleast one ester has a carbon chain distribution of the acid-derivedcomponent determined by gas chromatography (GC) according to ISO 5508with carbon numbers in the ranges of from 0 to 2.00%, preferably in therange of from 0 to 1.00%, more preferably in the range of from 0 to 0.5%C₆, in the range of from 3.00% to 10.00%, preferably in the range offrom 3.00 to 8.00%, more preferably in the range of from 4.00 to 7.00%C₈, in the range of from 3.00% to 10.00%, preferably in the range offrom 3.00 to 9.00%, more preferably in the range of from 5.00 to 8.00%C₁₀, in the range of from 50.00% to 94.00%, preferably in the range offrom 55.00 to 90.00%, more preferably in the range of from 60.00 to85.00% C₁₂, in the range of from 0 to 25.00%, preferably in the range offrom 5.00 to 20.00%, more preferably in the range of from 10.00 to20.00% C₁₄, in the range of from 0 to 5.00%, preferably in the range offrom 1.00 to 4.00%, more preferably in the range of from 2.00 to 4.00%C₁₆ and in the range of from 0 to 1.00%, preferably in the range of from0.01 to 0.90%, more preferably in the range of from 0.1 to 0.6% C₁₈. Theacid-derived component determined by gas chromatography of an esterrefers to the chromatographic equivalent of an acid, which would havebeen formed upon hydrolytic cleavage of that ester into an alcohol andan acid.

In another preferred embodiment of the process according to theinvention, the at least one ester has a carbon chain distribution of theacid-derived component determined by gas chromatography (GC) accordingto ISO 5508 with carbon numbers in the range of from 0 to 2.00%,preferably in the range of from 0 to 1.00%, more preferably in the rangeof from 0 to 0.5% C₆, in the range of from 0 to 10.00%, preferably inthe range of from 1.00 to 7.00%, more preferably in the range of from2.00 to 5.00% C₈, in the range of from 0 to 10.00%, preferably in therange of from 1.00 to 7.00%, more preferably in the range of from 2.00to 5.00% C₁₀, in the range of from 50.00% to 95.00%, preferably in therange of from 60.00 to 90.00%, more preferably in the range of from65.00 to 85.00% C₁₂, in the range of from 5.00% to 35.00%, preferably inthe range of from 8.00 to 30.00%, more preferably in the range of from10.00 to 25.00% C₁₄, in the range of from 0 to 5.00%, preferably in therange of from 1.00 to 4.00%, more preferably in the range of from 2.00to 4.00% C₁₆ and in the range of from 0 to 1.00%, preferably in therange of from 0.01 to 0.90%, more preferably in the range of from 0.1 to0.6% C₁₈. The acid-derived component determined by gas chromatography ofan ester refers to the chromatographic equivalent of an acid, whichwould have been formed upon hydrolytic cleavage of that ester into analcohol and an acid.

The invention also relates to a drilling composition obtainable by aprocess according to the invention and having at least one, preferablyat least two, more preferably at least three of the followingproperties:

-   γ1) a plastic viscosity (PV) measured at 50° C. according to the    herein described test method in the range from 15 to 75 mPa·s,    preferably in a range of from about 15 to about 60 mPa·s, more    preferably in a range of from about 15 to about 40 mPa·s, more    preferably in a range of from about 15 to about 30 mPa·s, yet more    preferably in a range of from about 15 to about 25 mPa·s;-   γ2) a yield point (YP) measured at 50° C. according to the herein    described test method in the range from 5 to 45 lb/100 ft² (about    2.4 to about 21.6 Pa), preferably in a range of from about 5 to    about 40 lb/100 ft² (about 2.4 to about 20 Pa), preferably in a    range of from about 6 to about 25 lb/100 ft², (about 2.9 to about 12    Pa), more preferably in a range of from about 8 to about 20 lb/100    ft², (about 3.8 to about 10 Pa);-   γ3) a gel strength (GS) measured at 50° C. according to the herein    described test method in the range from 4 to 25 lb/100 ft² (1.9 to    12 Pa), preferably in a range of from about 4 to about 15 lb/100 ft²    (about 1.9 to about 7.2 Pa), preferably in a range of from about 4    to about 10 lb/100 ft², (about 1.9 to about 4.8 Pa), more preferably    in a range of from about 4 to about 8 lb/100 ft², (about 1.9 to    about 3.8 Pa).-   γ4) viscosity values (Brookfield, RVT, determined according to    ASTM 2983) at temperatures of 0° C. to 5° C. of not more than 10    mPa·s, preferably of not more than 8 mPa·s and preferably in the    range of from about 2.0 to 5.0 mPa·s, more preferably in the range    of from about 2.5 to 4.5 mPa·s, yet more preferably in the range of    from about 2.7 to 4.0 mPa·s;-   γ5) storage stability at 20° C. of at least two weeks, preferably of    at least one month, more preferably of at least three months, more    preferably of at least six months, more preferably of at least one    year,    whereby the combinations of properties γ1)γ2), γ1)γ3), γ2)γ3),    γ1)γ2)γ3), γ1)γ2)γ3)γ4), γ2)γ2)γ3)γ5), γ1)γ2)γ3)γ4)γ5), are    preferred, whereby the property combinations γ1)γ2)γ3),    γ1)γ2)γ3)γ4), γ1)γ2)γ3)γ5) and γ1)γ2)γ3)γ4)γ5) are particularly    preferred.

The compositions according to the invention further preferably haveimproved lubricity compared to previous drilling compositions.

The invention also relates to the use of a composition according to theinvention or of a composition prepared according to a process accordingto the invention as a drilling fluid.

The invention also relates to a drilling system comprising a drill head,a drill string, a reservoir for drilling composition and a drillingcomposition according to the invention or prepared according to aprocess according to the invention.

The invention also relates to a process for making a borehole comprisingthe steps:

-   a1) providing a composition according to the invention or a    composition prepared according to a process according to the    invention,-   a2) drilling a hole in a subterranean formation;-   a3) circulating the composition provided in a1) at least partially    in the hole at least partially while drilling.

Suitable methods and equipment for drilling in step a2) are well knownto the person skilled in the art, as are methods and means, for exampleusing pumps, for circulating a drilling fluid according to step a3). Thedrilling composition according to the invention has been found to beparticularly advantageous, owing to the combination of properties suchas environmental compatibility and biodegradability, low toxicity,viscosity, rheological properties, while providing good lubricity andallowing a good penetration rate of the drill into the subterraneanformation.

The invention also relates to a process for conveying cuttings from ahole drilled in a subterranean formation, preferably a process forconveying cuttings from a hole drilled in a subterranean formation tothe surface, comprising the steps:

-   -   b1) providing a composition according to the invention or a        composition prepared according to a process according to the        invention,    -   b2) circulating the composition provided in b1) at least        partially in the hole.

It is preferred in the process for conveying cuttings from a holedrilled in a subterranean formation that the composition is circulatedat least partially while drilling the hole. The composition willgenerally be circulated by passing through the drill assembly and outvia the drill head, then passing back along the drill hole towards thesurface, conveying the cuttings in the flow.

The invention also relates to a process for treatment of a drill headcomprising the steps:

-   c1) providing a composition according to the invention or a    composition prepared according to a process according to the    invention,-   c2) circulating the composition provided in c1) at least partially    through the drill head at least partially while the drill head is    operated in a subterranean formation.

In a preferred embodiment of the process for treatment of a drill head,the treatment is at least one of cleaning, cooling and lubrication. Thedrilling composition according to the invention has been found to beparticularly suitable for such treatment owing to the combination ofhydrophilic and hydrophobic components comprised therein.

The invention also relates to a process for production of at least oneof oil and gas, comprising process steps:

-   d1) providing a composition according to the invention or a    composition prepared by a process according to the invention,-   d2) drilling at least one hole in a subterranean formation while at    least partially circulating the composition provided in d1) at least    partially in the hole;-   d3) obtaining at least one of oil and gas from the subterranean    formation at least partially by means of the at least one hole    drilled in d2);-   d4) optionally, subjecting the at least one of oil and gas to at    least one processing step selected from purifying, refining and    treating.

Steps d1) and d2) may be carried out by methods known to the skilledperson, as described above. Step d3) may also be carried out by methodsknown to the skilled person, and may comprise stages such as pumping,collecting, storing, and the like. Step d4) may be carried out at thesame location as the operation described by steps d1) to d3), or it maybe carried out at a different location. If step d4) is carried out at adifferent location to steps d1) to d3), in particular a differentlocation to step d3), the process will also comprise a step oftransporting or conducting at least one of oil and gas from the locationof at least step d3) to the location of step d4).

The invention is now more closely illustrated by means of examples,which are not intended to limit the scope of the invention.

EXAMPLES Test Methods Plastic Viscosity (PV), Yield Point (YP), GelStrength

Plastic viscosity, yield point and gel strength were measured using aFann® direct reading viscometer (Model 35 from Fann Instrument Company,Houston, Tex., USA) according to the method described in “RecommendedPractice for Field Testing of Oil-based Drilling Fluids”, UpstreamSegment, API (American Petroleum Institute) recommended practice 13B-2,Fourth Edition, March 2005, section 6.3, p. 8-10.

Electrical Stability

Electrical stability was measured using a Fann® electrical stabilitytester (Model 23D from Fann Instrument Company, Houston, Tex., USA)according to the method described in “Recommended Practice for FieldTesting of Oil-based Drilling Fluids”, Upstream Segment, API (AmericanPetroleum Institute) recommended practice 13B-2, Fourth Edition, March2005, section 10, p. 22-24.

Example 1

An oil phase was prepared by combining 249.4 ml of PureDrill® HT-40(Petro-Canada, Canada) with 13.1 ml of a 2-ethylhexyl ester of C₈-C₁₄fatty acids obtainable from Cognis Oleochemicals GmbH, Dusseldorf,Germany, under the trade name OMC 586. This oil phase was then combinedwith 4.2 g of EZ MUL® NT (from the company Halliburton (Baroid), Tex.,USA), 87.5 ml of a 25% (by weight) aqueous calcium chloride solution,3.5 g of DURATONE® HT (from the company Halliburton (Baroid), Texas,USA), 3.5 g of GELTONE® II (from the company Halliburton (Baroid), Tex.,USA), Tex., USA), and 280 g of barite. Rheological parameters weredetermined at 50° C. as shown in Table 1 under the heading “beforeageing”.

The mixture was aged by treatment in an autoclave in a Baroid rolleroven model 70040 at 121° C. (250° F.) for 16 hours according to themethod described in “Recommended Practice for Laboratory Testing ofDrilling Fluids”, API (American Petroleum Institute) recommendedpractice 131, Seventh Edition, February 2004/ISO 10416:2002 (modified),section 21, p. 66-73. The electrical stability and rheologicalparameters were then determined at 50° C. as shown in Table 1 under theheading “after ageing”.

TABLE 1 Before ageing After ageing Electrical stability (V) n.d. 490Measured values 600 rpm 49 50 300 rpm 30 31 200 rpm 22 23 100 rpm 14 15 6 rpm 5 6  3 rpm 4 5 Plastic viscosity (cP) 19 19 Yield point (lbf/100ft²) 11 12 Gel strength 10 s/10 min (lbf/100 ft²) 5/6 5/6 n.d. = notdetermined

Example 2

The same procedure was followed as that for Example 1, with thedifference that 26.2 ml of OMC 586 was used.

Example 3

To a composition consisting of 249.4 ml of PureDrill® HT-40(Petro-Canada, Calgary, Canada), 4.2 g of EZ MUL® NT (from the companyHalliburton (Baroid Fluid Services), Texas, USA), 87.5 ml of a 25% (byweight) aqueous calcium chloride solution, 3.5 g of DURATONE® HT (fromthe company Halliburton (Baroid Fluid Services), Texas, USA), 3.5 g ofGELTONE® II (from the company Halliburton (Baroid Fluid Services),Texas, USA), Texas, USA), and 280 g of barite, was added 13.1 ml of OMC586 (Cognis Oleochemicals GmbH, Düsseldorf, Germany).

Example 4

The same procedure was followed as that for Example 3, with thedifference that 26.2 ml of OMC 586 was added.

Example 5

The procedure of Example 1 was followed, with the difference that 1.5 gof the structure building agent GELTONE II was used. The yield point ofthe product before ageing by heat rolling as described for Example 1 was8 lb/100 ft². The yield point of the product after ageing by hot rollingas described for Example 1 was 10 lb/100 ft².

Example 6 Rate of Penetration (ROP)

Boreholes were drilled using the compositions of Examples 1 to 4 asdrilling fluid, and the respective rate of penetration measured asdistance per hour. The rock formation which was drilled into, thedrilling equipment, weight on bit, and rotation speed (rpm), weremaintained effectively constant for each test, so that the only variablewas the drilling fluid. In this way, comparative data were obtained forthe different compositions. The results are shown in Table 2.

TABLE 2 Penetration rate Example test result 1 very good 2 good 3satisfactory 4 satisfactory

Drilling into subterranean formations, whether onshore or offshore, isaccompanied by substantial costs. It is thus advantageous to reduceoverall drilling time. Penetration rate, while not being the sole factordetermining overall drilling time, provides a considerable contributionthereto. Faster penetration rates are therefore desirable. The aboveresults show that the composition according to the invention, and inparticular the use of the above-described esters in combination with asaturated hydrocarbon (paraffin) as described above, results in improvedpenetration rates when drilling, thereby contributing to reducingoverall drilling time.

1. A drilling composition comprising I) an organic phase comprisingcomponents i. from about 20 wt. % to about 99.999 wt. %, based on thetotal weight of components i. and ii., of at least one linear orbranched, cyclic or non-cyclic, saturated hydrocarbon, ii. from about0.001 wt. % to about 25 wt. %, based on the total weight of componentsi. and ii., of at least one ester, II) from 0 to about 50 wt. %, basedon the total weight of the composition, of water or aqueous phase, andIII) from 0 to about 60 wt. %, based on the total weight of thecomposition, of at least one additive, wherein the sum of the weightcomponents I) to III) is 100 wt. %.
 2. The drilling compositionaccording to claim 1, wherein the at least one hydrocarbon is at leastone alkane.
 3. The drilling composition according to claim 1, whereinthe at least one ester is at least one ester selected from the groupconsisting of esters formed from at least one C₁ to C₂₄ monocarboxylicacid with at least one mono-functional alcohol.
 4. The drillingcomposition according to claim 1, wherein the composition is in the formof an emulsion.
 5. The drilling composition according to claim 1,wherein the at least one additive is at least one additive selected fromthe group consisting of weighting agents, clays, fluid loss additives,pH modifiers, viscosity modifiers, filtration control agents,emulsifiers, salts, wetting agents, dispersants.
 6. The drillingcomposition according to claim 1, wherein the at least one ester has acarbon chain distribution of the acid-derived component determinedaccording to ISO 5508 with carbon numbers in the ranges of from 0 to2.00% C₆, from 3.00% to 10.00% C₈, from 3.00% to 10.00% C₁₀, from 50.00%to 94.00% C₁₂, from 0 to 25.00% C₁₄, from 0 to 5.00% C₁₆ and from 0 to1.00% C₁₈.
 7. The drilling composition according to claim 1, wherein theat least one ester has a carbon chain distribution of the acid-derivedcomponent determined according to ISO 5508 with carbon numbers in theranges of from 0 to 2.00% C₆, from 0 to 10.00% C₈, from 0 to 10.00% C₁₀,from 50.00% to 95.00% C₁₂, from 5.00% to 35.00% C₁₄, from 0 to 5.00% C₁₆and from 0 to 1.00% C₁₈.
 8. A process for the preparation of a drillingcomposition, comprising the steps: a) providing as component i. fromabout 20 wt. % to about 99.999 wt. %, based on the total amount of i.and ii., of at least one linear or branched, cyclic or non-cyclic,saturated hydrocarbon, b) providing as component ii. from about 0.001wt. % to about 25 wt. %, based on the total amount of i. and ii., of atleast one ester, and wherein the sum of the weight amounts provided ina) and b) is 100 wt. %, c) combining the at least one hydrocarbon andthe at least one ester.
 9. A process for preparation of a drillingcomposition, comprising the steps: A) preparation of an organic phasecomprising components i. from about 20 wt. % to about 99.999 wt. %,based on the total weight of components i. and ii., of at least onelinear or branched, cyclic or non-cyclic, saturated hydrocarbon, ii.from about 0.001 wt. % to about 25 wt. %, based on the total weight ofcomponents i. and ii., of at least one ester, B) preparation of anaqueous phase comprising from about 50 wt. % to 100 wt. % water, basedon the total amount of aqueous phase, C) combination of the organicphase prepared in step A) with from 0 to 50 wt. %, based on the totalweight of the composition, of the aqueous phase prepared in step B), andD) combination of at least one of the organic phase, the aqueous phaseand the combination of the organic phase and the aqueous phase with from0 to about 60 wt. %, based on the total weight of the composition, of atleast one additive.
 10. The process according to claim 9, furthercomprising the step E) homogenization.
 11. A process according to claim9, wherein the composition at the end of at least one of steps C), D) orE) is in the form of an emulsion.
 12. The process according to claim 11,wherein the emulsion is a nanoemulsion or a microemulsion with dropletsizes in the range from 5 nm to 1000 μm.
 13. The process according toclaim 8, wherein the at least one ester is at least one ester selectedfrom the group consisting of esters formed from at least one C₁ to C₂₄monocarboxylic acid with at least one monofunctional alcohol.
 14. Theprocess according to claim 8, wherein the at least one ester has acarbon chain distribution of the acid-derived component determinedaccording to ISO 5508 with carbon numbers in the ranges of from 0 to2.00% C₆, from 3.00% to 10.00% C₈, from 3.00% to 10.00% C₁₀, from 50.00%to 94.00% C₁₂, from 0 to 25.00% C₁₄, from 0 to 5.00% C₁₆ and from 0 to1.00% C₁₈.
 15. The process according to claim 8, wherein the at leastone ester has a carbon chain distribution of the acid-derived componentdetermined according to ISO 5508 with carbon numbers in the ranges offrom 0 to 2.00% C₆, from 0 to 10.00% C₈, from 0 to 10.00% C₁₀, from50.00% to 95.00% C₁₂, from 5.00% to 35.00% C₁₄, from 0 to 5.00% C₁₆ andfrom 0 to 1.00% C₁₈.
 16. A drilling composition obtainable by a processaccording to claim 8 and having at least one of the properties: γ1) aplastic viscosity measured at 50° C. according to the herein describedtest method in the range from 15 to 75 mPa·s; γ2) a yield point measuredat 50° C. according to the herein described test method in the rangefrom 5 to 45 lb/100 ft² (2.4 to 21.6 Pa); or γ3) a gel strength measuredat 50° C. according to the herein described test method in the rangefrom 4 to 25 lb/100 ft² (1.9 to 12 Pa).
 17. (canceled)
 18. A drillingsystem comprising a drill head, a drill string, a reservoir for drillingcomposition and a drilling composition according to claim
 1. 19. Aprocess for making a borehole comprising the steps: a1) providing acomposition according to claim 1; a2) drilling a hole in a subterraneanformation; and a3) circulating the composition provided in a1) at leastpartially in the hole at least partially while drilling.
 20. A processfor conveying cuttings from a hole drilled in a subterranean formation,comprising the steps: b1) providing a composition according to claim 1,and b2) circulating the composition provided in b1) at least partiallyin the hole.
 21. The process according to claim 20, wherein thecomposition is circulated at least partially while drilling the hole.22. A process for treatment of a drill head comprising the steps: c1)providing a composition according to claim 1, and c2) circulating thecomposition provided in c1) at least partially through the drill head atleast partially while the drill head is operated in a subterraneanformation.
 23. The process according to claim 22, wherein the treatmentis at least one of cleaning, cooling or lubrication.
 24. A process forproduction of at least one of oil or gas, comprising the steps: d1)providing a composition according to claim 1, d2) drilling at least onehole in a subterranean formation while at least partially circulatingthe composition provided in d1) at least partially in the hole; d3)obtaining at least one of oil and gas from the subterranean formation atleast partially by means of the at least one hole drilled in d2); andd4) optionally, subjecting the at least one of oil and gas to at leastone processing step selected from purifying, refining or treating.